Textile oil



United States 2,839,464 TEXTILE OIL Lorne W. Sproule, Sarnia, Ontario,and James H. Norton, Corunna, Ontario, Canada, assignors to EssoResearch and Engineering Company, a corporation of Delaware N0 Drawing.Application February 16, 1954 Serial No. 410,738

1 Claim. (Cl. 252-83) The present invention relates to an improvedtextile oil and to an improved method of treating certain textilematerials prior to dyeing. More particularly, the invention is concernedwith an improved textile oil which affords effective lubrication in alltextile processing operations and which may be readily removed byscouring prior to dyeing.

In brief compass, the invention pertains to a mineral oil base textileoil which contains dissolved therein small amounts of. threenon-ionizing components, to Wit a detergent, an emulsifying agent and acoupling agent, which have a synergistic effect on the solutionstability, emulsion stability and scouring efficiency of the oil. The

textile oil of the invention has particular utility in the treatment ofcertain raw animal fibres, such as raw wool, containing substantialproportions of lime or other alkaline metal compounds reacting withanionic materials to form salts of low water solubility.

The textile oils most commonly used heretofore are based on variousfatty oils of animal or vegetable origin. These oils are ratherexpensive and readily oxidizable. Mineral oils which are superior withrespect to availability and oxidtaion resistance cannot be used as suchbecause they are diificult to remove from the finished textiles byconventional scouring with Water containing soap and soda ash.

Many suggestions have been made prior to the present invention toimprove the utility of mineral oils for textile treating purposes bymeans of various modifying agents. Most of these improved oils containionizing emulsifiers or detergents of the metal sulfonate type alone ortogether with certain other emulsifier, rust preventives, Wetting orsurface active agents, such as sorbitan esters of fatty limed wool isnormally used. This W001, which is removed from the animal hides withthe aid of a depilatory agent such as lime, contains-large quantities offree lime. Textile oils and scouring baths used in. the manufacture offabrics from this type of wool must be lime resistant. Conventionaltextile oils and scouring baths are greatly deficient in this respect.The calcium ions present in the raw wool react with the anions of sodiumsulfonates and other soaps'of conventional Wool oils and with anions ofthe soaps of the scouring baths to form Water-insoluble soaps and salts.These insoluble compounds are adsorbed on the W001, forming a curd orscum which resists subsequent scouring and seriously interferes with thedyeing process. Similar complications arise when hard water is used inscouringall types of textiles treated WithiBXtlle oils containingconstituents which ionize in aqueous solutions to yield anionsformingwater-insoluble compounds with calcium or thelike. The, presentinvention-oven atent Thirdly, the oil must be easily removable byscouring I with distilled and hard water scouring baths.

It has now been found that all these requirements are adequately met bya mineral base textile oil which is substantially free of constituentsionizing in aqueous solutions to yield ions forming compounds of lowwater solubility with calcium or the like and which contains smallproportions of three non-ionizing oil-soluble components acting as adetergent, an emulsifier and a coupling or stabilizing agent,respectively. These three non-ionizing components have a synergisticeffect upon each other and the mineral oil base with respect to theiroil solubility, the detergency and the emulsion stability of thefinished textile oil.

Compounds suitable as the detergent component of the textile oil of theinvention are the polyglycol esters of unsaturated high molecularweightfatty acids having the general formula wherein R is an unsaturatedaliphatic radical having 14-22 carbon atoms, more specifically 16-18carbon atoms, n is an integer of from 2-6, more specifically 2-4, and xis an integer offrom about 5 to about 30, more specifically 5-15. Inaccordance with the preferred embodiment of the invention, R is thehydrocarbon radical of oleic acid, 11 is 2 and x averages about 13. Aproduct of this type is now on the market under the trade name AntaroxAgent 377-AE (Chemical Developments of Canada Ltd.; General DyestuifCorp. U. S. A.). These products are probably mixtures composed chieflyof the mono-ester with some di-ester present. A concentration of about0.5-20 wt. percent, preferably about 5-15 Wt. percent, of thiscomponent, based on mineral oil, may be used. i

The emulsifier component of the textile oil of the invention is apolyether alcohol of the general formula wherein R is an aryl, aralkylor saturated or unsaturated alkyl group having 10-20, more specifically14-16, carbon atoms, n is an integer of 2-6, more specifically 2-4, andx is an integer averaging about 2-20, more specifically 2-6. Thepreferred-emulsifiers are alkyl-aryl polyether alcohols in which R isessentially nonyl phenyl, n is 2 and x averages about 4%. A product ofthis type is on the market under the trade name Triton X-45 (Rohm andHaas Co.) which is essentially an alkylated aryl polyetheralcohol havingthe general formula r of the latter.

The coupling or stabilizing agent of the textile oil of the invention isan oil-soluble unsaturated fatty acid partial ester of a higherpolyhydric alcohol of the type disclosed in the MacLaurin Patent No.2,404,240. The preferred coupling agent of the invention is sorbitanmono-oleate which may be used in concentrations of about 1-10 wt.percent, preferably about 2-6 wt. percent, based on mineral oil. Theconcentration of the coupling agent in the finished textile oil shouldlikewise be substantially below that of the detergent component andshould not exceed about 50% of the latter.

In general, it has been found desirable to add a small 4 (Triton X-45)and the coupling agent was sorbitan mono-oleate.

The difierent textile oils were tested for their solution stability andemulsion stability as follows. The solution stability was tested,storing the freshly prepared samples in sealed glass bottles at roomtemperature and observing visually the degree of separation after 1, 7and 30 days of storage. The emulsion stability was measured by adding 10mls. of oil to 90 mls. of the proportion of about 0.05-2 wt. percent,preferably less 10 test water in a glass stoppered graduate, shaking for1 than 1 Wt. percent, say about 0.5-0.8 wt. percent, of minute and thenallowing the solution to standfor 24 water to the textile oil. Suchsmall amounts of water hours. The number of mls. of oil or creamseparating cooperate with the coupling agent in increasing the from theemulsion within this time was recorded. The compatibility of the othercomponents with the mineral composition and properties of the oilstested are sumil b 15 marized in Table I below.

Table I Designation B21 B-7 13-23 13-22 13-1 13-20 13-16 13-8 B-B B910Formula, weight percent: Antarox agent377-AE l 6 6. 5 8 10 11.3 12. 5 1510 10 Triton X45; 3 3 3 3 3 3 3 3 1. 5 4. 5 Sorbitan mono-o1eate 4 4 4 44 4 4 4 4 4 er 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0,7 Mineral oil 01. 387. 3 85.8 84. 3 82. 3 81. 79. 8 77. 3 83. 8 8018 Solution stability:

1 day at room temp Clear Clear Clear Clear Clear Clear Sep. Sep. ClearClear 7 days at room temp Clear Clear Clear Clear Clear Scp. Clear Clear30 days at room temp Clear Clear Clear Clear Clear Clear Clear Emulsionstability (cc. sep'n./24 hrs):

Dist. water 15 0 0 0 0 0 2 0' 300 p. p. in. hard water. 13 4 0 0 0 0. 0600 p. p. in. hard water". 10 15 0 0 0 0 0. 1,200 p. p. in. hard water 0Designation B-l7 B-4 13-5 B15 3-13 13-11 B-14 13-3 13-2 Formula, weightpercent:

Antarox agent 377-AE 10 10 10 10 10 10 5 Triton X 6 3 3 3 3 3 1.5 6Sorbitan mono-cleats. 4 4 2 2 8 \Vatep 0. 7 0. 7 0. 7 0. 35 It Mincral01L 79. 3 90 97 87 83 84. 3 86.3 91. 1 64.5 Solution stabilit 1 day atroom temp Sep 1 Sep 1 Hazy Sep. Sep Sep. Sep. Sep Clear 7 days at roomtemp l Hazy Clear 30 days at room temp Clear Emulsion stability (on.sepn./24 hrs):

Dist. water a o 300 p. p. m. hard water 0 600 p. p. in. hard water..-".0' 1,200 p. p. in. hard Water 1 0.7% water does not clarify solutions.1 Almost transparent emulsion.

The mineral oil base of the textile oil of the invention It will be seenfrom the above data that stable soluinay be any mineral oil distillatehavinga viscosity of tions are formed using from 1-10 wt. percent of theabout -200 SSU at 100 F. Relatively light oils obtained from naphthenicor paraffinic base stocks, such as Mid-Continent crudes and having aviscosity of about 75-150 SSU at 100 F. and a viscosity index of about50-100 are preferred. I

' The invention will be further illustrated by the following specificexamples.

EXAMPLE I detergent of the invention (Antarox Agent-377-AE)'at constantconcentrations of emulsifier (Triton X-45), coupling agent (sorbitanmono-oleate) and water at 3 wt. percent, 4 wt. percent and 0.7 wt.percent, respectively (Formulae B-21, B-7, B-23, B-22 and B-1). FormulaeB-9 and 3-10 show that a range of from 1.5-4.5 wt. percent of theemulsifier used forms stable solutions for given concentrations of theother ingredients. A stable solution was also formed when theconcentration of the ingredients of Formulae B-l were doubled as shownin Formula B-2.

It is also significant that the detergent and emulsifier were notsoluble in the mineral oil either alone or together, as shown inFormulae B-4, B-5, and B-IS. However, these components become soluble inthe presence of the coupling agent of the invention as shown by theother formulae.

The above data also show that stable emulsions as well as stablesolutions are obtained in accordance with the invention. This isdemonstrated by Formulae B-1 and 3-2 for a wide range of componentconcentrations. Formulae B-9 and B-10 show that stable emulsions areobtained at emulsifier concentrations as low as 1.5 wt.

percent and as high at 4.5 wt. percent in oilsof the type of FormulaB-l.

EXAMPLE II.

Two textile oils of the type of Formula B-l of Example I were preparedas described in Example I with the exception that the detergent of oneoil was a polyglyeol ester of oleic acid containing moles of ethyleneoxide per mole of acid (Antarox Agent 377-BK) and the detergent of theother, oil was a polyglycol ester of oleic acid containing 8 molesoiethylene oxide ,per mole of acid (Antarox Agent 377-LE). The mineraloil was the same as that used in Example I. These oils were tested asdescribed in Example I. The composition and properties of these oils arecompared with those of Formula 3-1 in Table II below.

Table II Designation 3-18 3-19 B-l Formula. weight percent:

Antarox agent I3177-13 K. 10...

Triton X-45 3. Sorbitan mono-cleats 4 4. Water 0.7. Mineral oil 82.382.3... 82.3. Solution stability:

1 day at room temperature. Hazy Clear Clear 7 days at room temperatureS1. hazy .-do. Do.

30 days at room temperature slhsepara- .do Do.

on. Emulsion stability (cc. sep'n. in 24 hours):

Distilled water 20 0 O.

300 p. p. m. hard water 0.

600 p. p. in. hard water-" 0.

1,200 p. p. in. hard water. 0.

The data of Table II show that at the 10% concentration level only thehighest molecular weight detergent is capable of forming stableemulsions, particularly in hard water (Formula B-l), thus demonstratingthe superiority of this detergent over lower molecular weight compounds(Formulae 13-18 and B-l9) in this respect.

EXAMPLE III A prior art type mineral oil base textile oil was comparedwith an oil of the present invention (Formula B-l of Example I) forsolution stability, emulsion stability and scourability. The prior artoil contained 12 wt. percent of sodium sulfonate and 1.8 wt. percent ofTween 81 (Atlas Powder Co.) which is a polyoxyethylene sorbitanmono-oleate containing about 8 moles of ethylene oxide per 1 mole ofsorbitan mono-oleate and about 86 wt. percent of a solvent refinedMid-Continent type distillate of 100 SSU viscosity at 100 F. and 90Viscosity Index.

The solution and emulsion stability was measured as described in ExampleI. The scourability was evaluated by the Ontario Research Foundation (0.R. F.) method described in U. S. Patent No. 2,565,403 of Sproule andDixon which is as follows:

A 20 gram sample of cloth, previously extracted with ether, is oiledwith 10% of its weight of oil. The sample is placed in a 4 litre jartogether with 1 litre of scouring solution. The scouring solution iscomposed of 0.2% soap and 0.1% soda ash. The jar is then placed in aframe capable of rotating about its central axis at 50 R. P. M. Theduration of the test is 1 hour at a temperature of 110 F. Afterscouring, the sample of cloth is rinsed, dried and the oil contentdetermined by ether extraction. The residual oil content is expressed asthe percentage of the original oil applied.

In addition to this standard test, four other scouring tests were usedto evaluate the non-ionic wool oils. These tests were modifications ofthe standard method using distilled and hard water with a syntheticdetergent replacing the conventional anionic soap. Sodium chloride wasadded in one case to simulate actual plant practice in which it is usedas a synergistic builder to aid the detergent in scouring the wool. Thesynthetic detergent was technically pure sodium lauryl sulfate. Theresults of these experiments are summarized in Table III below. i

Table III Designation Formula, weight percent:

odium suhonate- Tween 8l Mineral oil V. I.)..

b-H 888 can: 0

M P' s s s O M NDFU! Dec 6 1 U. S. Navy hard Water, 300 p. p. m.hardness: (Ca Cir/21120 0.2345 gum.) or litre of (Mg Ch/GH O 0.2680gms.) distilled water.

I 0.2% soap and 0.1% soda ash in distilled water at F. for 1 hour.

I 0.25% sodium lauryl sulfate in distilled water.

10.25% sodium lauryl sulfate and 0.5% sodium chloride in distilled weer.

' N 0 separation.

b 011 and cream.

v Oil.

The data of Table 111 show that both oils produce stable emulsions indistilled water and 300 p. p. m. synthetic hard water. However, theconventional anionic wool oil shows some oil separation at 600 p. p. m.hard water and complete oil separation at 1200 p. p. m. hard water. Thenon-ionic wool oil of the invention forms stable emulsions up to 1200 p.p. m. hard water. In the case of the anionic-wool oil of the prior art,the calcium and magnesium ions in the hard water are reacting with thesulfonate to form insoluble soaps, thus depleting the emsulsifier. Thisextreme degree of hard water is at times encountered in mills wherelimed wool is employed.

The data also show that the prior art oil in. the O. R. F. standardscouring test using distilled water, 0.2% soap and 0.1% soda ash gives27% residual oil whereas the non-ionic oil of the invention gives 23.5%oil. In the detergent scour using distilled water and 0.25% syntheticdetergent, the prior art oil and the oil of the invention show 25% and16.4% residual oil, respectively. When 0.5% of sodium chloride is addedto the detergent scour, the non-ionic oil of the invention gives only9.2% residual oil whereas the anionic prior art oil shows 20% oil leftin the cloth.

In synthetic hard water, the non-ionic wo'ol oil is vastly superior tothe anionic oil, giving 8.2% and 5.0% oil in 300 p. p. m. and 600 p. p.in. hard water, respectively, compared to 26 and 23% residual oil forthe anionic oil.

It will be understood that various modifications may be made in thecomposition of the textile oils within the spirit of the invention. Theinvention also embraces the improved process for oiling various textilefibres, yarns and fabrics, particularly textiles of the type of limedwool with the textile oils of the invention and scouring such textileswith distilled water or water of any hardness References Cited in thefile of this patent UNITED STATES PATENTS 1,970,578 Schoeller et a1 Aug.21, 1934 8 Steindorf et a1. Sept. 2, 1940 MacLaurin July 16, 1946Sproule et al Aug. 21, 1951 Jeiferson Sept. 28, 1954 OTHER REFERENCESAtlas Surface Active Agents, Atlas Powder Company, 1950 (Table No. 1),and page 24.

